New dyestuffs containing sulphur



Patented Feb. 21, 1933 UNITED 1 STATES PATENT OFFICE RICHARD HERZ, 0F FBANKI'ORT-ON-THE-MAIN, AND MAX SGHUBER'I." AND WILHEIM HECHTEN'BERG, OF FBAN'KFORT-ON-THE-MAIN-FECHENHEIM, GERMANY, .AS- I SIGNORS T0 GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION or DELAWARE NEW DYi STUFFS CONTAINING SULPHUR n Drawing. Application filed February 1, 1932, Serial No. 590,310, and in Germany March 2a,,19a1g Our present invention relates to new dyestuffs containing sulphur.

In U. S. specification Serial No. 590,309 applied for by Richard Herz and Max Schu- "6 bert and filed on the same date, new-indophenols of the benzocarbazole series are described which correspond to the general formula I N m. Lo.

15 nucleiI or II or I an I II" are replaced by the benzo nucleus V p j R meanshydrogen or alkyl' and all nuclei may contain as substituents methyl, methoxy, chlorine, hydroxy or a sulphonic ac d group. According to the present invention these indophenols or their leuco compounds are treated with sulphurizing agents, especlally v with an alcoholic polysulphide solution of a.

'30 high content of sulphur.

wherein two adjacenth drogen atoms of the fastness. By this greenish tint the new dye-' Ewaxm'ple 1 10 parts of the leuco-indophenol' of the probable formula are boiled for 50-70 hours in an apparatus provided with a reflux condenser with an alcoholic polysulphide prepared from 10 parts of concentrated sodium sulphide, 12 parts of sulphur and 50 parts of alcohol. When the reaction is finished the alcohol is distilled off. The residue is freed from sulphur in the usual manner, washed and dried.

Y The dyestufi' thus obtained dissolves in concentrated sulphuric acid with a pure blue color. It dyes cotton from the hydrosulphite vat greenish blue shades. A similar, but more greenish dyestufl' is obtained by adding a copper salt to the mass.

Emample 2 .7

When the leuco-.indophenol of the 9.-ethyl- 1.2-benzocarbazole of the probable formula Example 1 a dyestuif is obtained, dyeing cotton from the sodium sulphide bath pure green shades.

The N-methyl-homologues yields a similar dyestuff.

Emample 5 10 parts of the leuco-indophenol corresponding to the probable formula are boiled for about 50 hours in an apparatus provided with a reflux condenser with an alcoholic polysulphide solution, prepared from 17 parts of concentrated sodium sulphide, 22.5 parts of sulphur and 100 parts of ethanol with the addition of 2.7 parts of copper sulphide. When the reaction is finished the ethanol is distilled off. The residue is freed from sulphur in the usual manner, washed and dried. The dyestuff thus obtained dissolves in concentrated sulphuric acid with a pure blue color and dyes cotton from the sodium sulphide bath blue-green shades.

Emwtple 4 10 parts of the leuco-indophenol-sulphonic acid of the probable formula 20 parts of crystallized sodium sulphide, 9 parts of sulphur, 10 parts of water and 5 parts of crystallized copper sulphate are concentrated by evaporation until a melting point of 107 and then boiled for 30 hours in an apparatus provided with a reflux condenser. The melting is diluted with water and after the addition of 4 parts of crystallized sodium sulphide the separated dyestulf is filtered, washed, acidified and dried.

The dyestuif obtained in this manner dissolves in concentrated sulphuric acid with a dark-green color. It dyes cotton from the sodium sulphide bath bluish black shades.

In an analogous manner the other indophenols or leuco-indophenols described in the aforesaid copending application may be converted into corresponding greenish dyestufis.

We claim: 1. As new compounds the dyestuffs containing sulphur, prepared by treating an indophenol of the benzocarbazole series of the general formula I II (wherein two adjacent hydrogen atoms of the nuclei I or II or I and II are replaced by the benzo nucleus (wherein R means hydrogen or ethyl) with sulphurizing agents in the presence of copper which compounds dye from the sodium sulphide bath or from the vat greenish blue to green shades of a good fastness.

3. As a new compound the dyestuif containing sulphur, prepared by treating the leuco-indophenol of the probable formula with sulphurizing agents in the presence of copper which compound dyes from the hydrosulphite vat greenish blue shades.

at. As a new compound the dyestuif containing sulphur, prepared by treating the leuco-indophenol of the probable formula OYQS with sulphurizing agents which compound dyes from the hydrosulphite vat bluish green shades.

5. As a new compound the dyestufi containing sulphur, prepared by treating the leuco-indophenol of the probable formula Hall:

with sulphurizing agents which compound dyes from the sodium sulphide bath pure green shades.

In testimony whereof, We affix our signatures.

RICHARD HERZ. MAX SGHUBERT. WILHELM HEGHTENBERG. 

